Method of preparedg washing



I .nuc leuslof inorganic material and a coatingof k V Ineutral,- reaction:set sa lt 9f asynthetic organic, acidic United States Patent METHOD OF PREPARING WASH ING COMPOSITION Vladimir Dvorkovitz, Kansas City, Mo., and Jerome Arthur Goldman, Evanston, Ill., assignors to The Diversey Corporation, Chicago, Ill., a corporation of Illinois No Drawing, Filed 'Aug. 13, 1957, Ser. No. 677,853

8 Claims. ,(Cl. 2 52-4138 ganic alkaline material with a normally slow-reacting member of the classconsisting of higher alkyl aryl sulfonic acids, higher alkyl sulfonic acids, higher alkyl sulfuric acid esters, and admixtures thereof in the presence of a small amount of reaction promoting liquid, whereby said member is completely reacted with said alkaline material and a dry, solid, coated, finely divided detergent composition is produced at once'during the neutralization reaction. 7

The term normally; slow-reacting herein refers to the fact that when the particulate alkaline material is sprayed with the acidic wetting agent, in the above pro cess,'in the absence of the reaction promoting liquid, the wetting'agent slowly reacts with the alkalinematerial.

This application is a continuation-impart of our copending application Serial No. 427,677, filed May 4, l954, now abandoned, which, in .turn, was a continuation-in-part'of our copending applicationSeria-l No. 348,- 512, filed Ap i 1953; ne .Qbfilldpmd. Although synthetic organic, acidic wetting agents from the :class consisting of higher alkyl aryl sulfonic acids, higher alkyl sulfonic ,acids, higher alkyl sulfonicacid "ice ing member of the class consisting of higher alkyl aryl sulfonic acids, higher alkyl sulfuric acid esters, higher alkyl sulfonic acids, and admixtures thereof in the presence of a small amount of reaction promoting liquid '(e.g.,.glyco1, alcohol, sulfuric acid), whereby said memher is completely reacted with the alkaline material and a dry, solid, coated, finely divided detergent composition is produced atonce during the neutralization reaction. By spraying an excess of inorganic alkaline material with the synthetic organic, acidic wetting agent, some of the inorganic alkaline material will remain unreacted after all the organic wetting agent has been neutralized. The excess unreacted alkaline material serves as an inorganic detergent builder. This process may becarried out in a closed, horizontally extendingreaction vessel having horizontally rotating mixing paddles therein v liquid, a free-flowing product will not be produced, iustead a discolored (i'.e., brown) gummy mass will result;

and a stationary, horizontally extending, overhead pipe with spray nozzles which spray the liquid material on to the alkaline material. It is preferable to premix the reaction promoting liquid with the acidic wetting agent, although each of these constituents may be separately applied to the particulate alkaline material.

The reaction promoting liquid thus serves to enable the acidic Wetting agent to promptly'and' complet l react with the" inorganic alkaline material to form solid, -free-fiowing particles having improved detergency and obviates" the need for a drying step. In the event the inorganic alkalinematerial is sprayed with the organic acid material in the absence of the reaction-promoting in addition, the reaction between the inorganic alkaline detergent and acid etting agent will continue over an extended period of time which may .e nc ompass several days or more, whereas complete neutralizationmay be eliected in our proces in about 3-5 minutes.- i

V a Our process produces a Washing composition that is in thecform of finely divided particles, each of which comprises a nucleus of inorganic alkaline material surrounded by the neutralized reaction product i.e.-, salt) produced by the interaction of theacidicwetting agent esters, and admixtures thereof have some detergent propreaqti on products must be dried (e.g.,"in drum dryers) in order to volatilize the water. After such products. are

dried, they must be ground in order to producea finely' divided, free flowing detergent 'product. 1 'We have discovered a process by which the normally slow-reacting synthetic organic, acidic wetting agent rapidly and completely reacts with the inorganic alkaline material t harm a parti ulate .compcsitiofi rwit q ti I quiring eithera separate'drying step or grindingthe 7 reaction product. This heterogeneous process for pro- 'ducing a particulate" detergentcomposition havingwa,

e t ie i.

withv-aiportion'of the alkaline material. Thus, the pH of the particles as a whole ismarkedly in excess of the" H sl za isstiss .srea t eo Thi Q nables the particles tojbe added to waterto form a soluon to the particulate alkaline materiaL. For example, liquids may be used,'such"as ethyl alcohol, rretliyl'ia' lco hol, isopr'o'pyl alcohoLjbutyl alcohol, .ethyleneglycol, diethylene glycol, propylene,gly' gg'ol, and, 'other1similar water-soluble organicc'ompounds, wl iich increalse the realc and/or su tur caqi s to p wetting agent, 7 comprises: spraying i solid particulate Linaction between the -synthetic;organ-1 tion having. a .pH below about 8 during the period that the, particles are being hand agitated in-thefvvate'riand are in direct contact with the skin: Under conditions, subsequent roughe ning and ehapping-. of the hands are lessened. g x l The term reaction promotingliquid includes glycols,

alcohols, sulfuricacidandadmixtures thereof, whiiihlmay be sprayed with the synthetic organid acidic wettiugagent 's s t f hwartin asse w kthe p iu lkali'ne material. We prefer toemploy fd th der Propy yc rathenthanrolaftileji mate to minimize tire hazards. Although minor-amounts of j water as well as admixtures of was? ths wl sad .21:

and theIalkaline material'," thejus'e of water req careful controls,-since excessiveleyels thereof a formation of a gummy undivided mass; on the other hand, alcohols, glycols, and sulfuric acid do not require such careful control of the levels used. Thus, water is clearly distinguishable from the glycols, alcohols, sul furic acid, or aqueous dilutionsthereof, and its use is restricted to corlditionswhich permit very careful control of the level present inthe mix of alkaline material and synthetic organic, acidic wetting agent.

The synthetic organic wetting agent is restricted to member of the class consisting of higher 'alkyl aryl sulforiic acids, higher alkyl sulfonic acids, higher alkyl sul- {uric acid esters, and admixtures thereof. For example, such wetting agents include dodecyl benzene sulfonic acid, mahogany acids, octadecyl sulfuric acid ester, lauryl sulfuric acid ester, .dodecyl sulfonic acid, and the like. The inorganic alkaline .material serves to neutralize the synthetic organic, acidic wetting. agent and the excess um'eacted portion, which constitutesthe nucleus of our particulatedetergent composition, serves as a detergent builder. I This alkaline material may include such inorganic alkalies as caustic, sodium carbonate, sodium tripolyphosphate, sodium silicates,,sodium bicarbonate, any of the other alkalies employed in the detergent field, and admixtures thereof.

The following samples are typical particulate detergent compositions of this invention which employ a sulfonic acid as the synthetic organic, acidic wetting agent. An admixture of the wetting agent and reaction promoting liquid were sprayed on the particulate inorganic material.

Samples Particulate Inorganic MaterialL Wettin Agent:

Reaction. PromotlngLlquid Sulfuri Acid Particulate Inorganic Material: Perce Soda Ash Light Na Om) 59. 27 Sodium 'Iripolyp osphetecarboxymethyl Cellulosen;

Wetting Agent:

Dodecylbenzene Sulfonic Acid Reaction Promoting Liquid:

Sulfuric Acid Diethylene Glycol Percent N W r 9 5 Particulate Inorganic Materiel:

Soda Ash,'Light Sodium Bicarbonate.

Sodium Tripolyphosphate Wetting Agent; I V Dodecylbenzene Suli'onic Acid Reaction Promoting Liquid: a

S or Acid I 'Dicthylene G1yeol.

Particulate Inorganic Material- Soda. Light; Trisodium Phosphate, Sodium Metasilicate Pentahydrete...

- G Silicate (high SiO 'to N820 (content).'.

Wetting Agent:

Dodecylbenzene Suli'onic Acid Reaction Promoting Liquid: I

Sulfuric Acid U Diethylene Glycol NNNCO IN H DOOM H (O pa e-- Tetrasodium Pyrophos hate; Trisodium Phosphate, ines Sodium Metasilicete Pentahydrate Olate Flakes (oleic acid-containing soap) Soda Ash, Light Wetting Agent:

.Dodecylbenzene Sulfonic Acid Reactiltlifn'lromoting Liquid:

S uric Acid -Diethy1ene Glycol rteo: :noocio N on -10 lmooco on no Particulete Inorganic Materiah Soda Ash, Light--. Sodium Bicarbonat Sodium Tripolyphosphato,

l Do ecylbenzeneSulionic Acid... H

0 Diethylene Glycol Samples Particulate Inorganic Material: 7 Percent Percent Sodium Tripolyphosphcte, Gran a. 22. Sodium Metasilicate Pentahydrate, Gran.. 16.00 16. 00 Oarboxymethyl Cellulose, Low Viscosity (Hercules 0'1 Grade) 0. 23 0.23 Soda Ash, Dense 48. 27 4B. 27 Soda Ash, Light 10.00 10.00 Wetting Agent: i

Dodecylbenzene Sulfonic Acid 2. 38 1 12 Reaction'Promoting Liquid:

Sulfuric Acid 0. 42 1.08 Diethylene Glycol 0. 70 0.70

Particulate Inorganic Material:

Sodium Tripolyphosphate, Gran 10.00 10. 00 Soda Ash, Dense..- 65. 00 65. 00 Soda Ash, Light 20.00 20.00 Wetting Agent:

Dodecylbenzene Sulfonic Acid 3. 40 1.60 Reaction Promoting Liquid: 1 I

Sulfuric Acid 0. 60 2. 40 Diethylene Glycol 1.00 1.00

Particulate Inorganic Material Sodium Tri 10.00 Soda Ash, Light 65.00 Wetting Agent:

Dodecylbenzene Sulionic Acid 10.00 Reaction Promoting Liquid:

Sulfuric Acid 16.00

Particulate Inorganic Material;

Sodium Tripolyphosphate, Gran 10. 00. 10.00 Soda Ash, ight. 55.00 55. 00 .Wetting Agent: v y Dodecylbenzene Sulfonic Acid 25. 12 00 Reaction Promoting Liquid:

Sulfuric Acid 4. 50 18. 00 Ethyl Alcohol 6. 00 5. 00

Particulate Inorganic Materiel: Soda Ash, Light 54.00 A 54. 00 Sodium Carboxymcthyl Cellulose l. 00 1.00 Wetting Agent:

Dodecylbenzene Sulfonlc Acid 34. 00 16.00 Reaction Promoting Liquid: 7

Sulfuric Acid... 0.00 24.00 Ethyl Alcohol 5.00 5. 00

Typical formulations of this invention employing a suluric acid ester which have been prepared successfully in accordance with the new method of this invention and which serve as excellent detergents are Samples Particulate Inorganic Material: Percent Soda Ash, Light NSC/Q3) 59.

Sodium Tripolyp osphate... 28.00 Oerboxymethyl Cellulose 0.23 Wetting Agent:

Octadecyl sulfuric acid ester. 8. 50 Reaction Promoting Liquid:

Sulfur c 1 50 Diethylene Glycol 2-50 Particulate Inorganic Material:

Soda. Ash, Light Sodium Bicarbonate Sodium Metasllicate Pentahydrate" Sodium Tripoiyphosphate Wetting Agent:

. Octadecyl sulfuric acid ester Reaction Promoting Liquid:

' Sulfuric Acid i Diethylene Glycol 1 v Sulfuric Acid-- Diethylene Glycol........................................

Samples Particulate Inorganic Material:

Tetrasedium Pyrophos hate Trisodrum Phosphate, ines Sodium Metasilicate Pentahydrate Olate Flakes Soda Ash, Li ht Wetting Agent:

Octadecyl sulfuric acid ester Reaction Promoting Liquid:

uliurie Acid. Diethylene Glyml Percent to P9 2*.9 \rus co moo one on 000 Particulate Inorganic Material:

Soda Ash, Li ht Sodium Bicar Sodium Tripolyphosphate, Gran 15.00 Wetting Agent:

Octadecyl sulfuric acid ester Reaction Promoting Liquid:

Sulfuric Acid 0. 63 Diethylene Glyr-nl 0.20

Particulate Inorganic Material:

Sodium Tripolyphosphate, Gran Sodium Metasilicate Pentahydrate, Gran OaGrbozymethyl Cellulose, Low Viscosity (Hercules 0'1 ra Soda Ash, Dense Soda Ash, Li ht Wetting Agent:

Octadecyl sulfuric acid ester Reaction Promoting Liquid:

111111110 Avid Diethylene Glyml Particulate Inorganic Material:

Sodium Trlpolyphosphate, Gran Soda Ash, Dense Soda Ash, Tiirr'l'lf Wetting Agent:

Octadecyl sulfuric acid ester Reaction Promoting Liquid:

Sulfuric Acid- Diet-hylene Glyml to wona:

g-go 9: 9 09 go Formulations containing substantially the same ingredicuts and portions as those of Samples 1, 3, 5, 7, 9, .11, 13, and 20-26 were prepared except that in each case ethyl alcohol was employed in place of the diethylene glycol reaction promoting liquid. The resulting coating about the nucleus of particulate alkaline material did not retain the reaction promoting liquid since the ethyl alcohol was evaporated by the heat of reaction.

Formulations were prepared which contained the same ingredients and proportions of Samples 20-26, however,

laurylsulfuric acid ester was substituted for oc'tadecyl sulfuric acid ester.

' Formulations were also prepared'which contained substantially the same ingredients and proportions as those,

of Samples 20-26, Withthe exception that the levels of wetting agent were decreased 53% of the indicated values and the levels of sulfuric acid were increased 300% of the indicated values. v

Formulations were also prepared which containedsubstantially the same ingredients as Samples 1, 13, 20 and 26, except that the indicated levels of wetting agent conthe acidic wetting agent. The level of synthetic organic, acidic wetting agent may be at low as 0.5% by weight of the reaction mixture and as high as about 45-50% by weight of said.mixture.

The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications will be obvious to those skilled in the art.

We claim:

1. The processof producing a particulate detergent composition consisting essentially of a nucleus of inorganic material and a coating of a relatively neutral, reaction-set salt of a synthetic organic, acidic Wetting agent, which comprises: spraying solid particulate inorganic alkaline material which serves as a detergent builder with about 05-50% by weight, based on the weight of the reaction mixture, of a substantially anhydrous normally slow-reacting member of the class consisting of higher alkyl aryl sulfonic acids, higher .alkyl sulfonic acids, higher alkyl sulfuric acid esters, the alkyl groups in said sulfonic acids and said sulfuric acid esters containing about 12-18 carbon atoms and admixtures thereof in the presence of at least about 20% by weight, based on the Weight of said reacting members, of a substantially anhydrous reaction promoting liquid consisting essentially of a member of the group consisting of lower alkylene glycols having about 2-4 carbon atoms, lower alkyl alcohols having about 1-4 carbon atoms, concentrated sulfuric acid, and admixtures thereof, whereby said member is completely reacted with said alkaline material during a period of up to about 5 minutes and a dry, solid, coated, finely divided detergent composition is produced at once during the neutralization reaction.

2. The process of claim 1 wherein the reaction promoting liquid is concentrated sulfuric acid.

3. The process of claim 1 wherein the reaction promoting liquid is a lower alkylene glycol having about 2-4 carbon atoms.

4. The process of claim 1 wherein the reaction promoting liquid is diethylene glycol.

5. The process of claim 1 wherein the reaction promoting liquid is propylene glycol.

6. The process of claim 1 wherein the reaction promoting liquid is a lower alkyl alcohol having about 1-4 carbon atoms.

p 7. The process of claim 1 wherein said inorganic alkaline material consists essentially of at least one member of the group consisting .of caustic soda, soda ash, sodium silicates, sodium bicarbonate, and sodium phosphates.

8. The process of claim 1 wherein said inorganic alkaline material contains soda ash.

References Cited in the file of this patent UNITED STATES PATENTS 1,989,765 Moss p Feb. 5, 2,243,054 .Vail May 20, 1941 2,287,864 I Burton June, 30, 1942 2,351,559. Treflder" June 13, 1944 2,356,443 ',Bissinger Aug. 22, 1944 2,390,406 Wegst etal. 'Dec. 4, 1945 2,465,346 -Bodman Mar. 29, 1949 2,730,507 Bradford. Jan. 10, 1956 2,766,276 Kolling Oct. 9, 1956 2,767,146 I Bonewitz et a1. Oct. 16, 6 2,776,943 Eaton Jan. 8, 1957 4 2,791,562 1957 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, $982,736 I May 2, 1961 Vladimir Dvorkovitz et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent. should read as "corrected below.

Column 6, line 24 for "members" read member Signed and sealed this 19th day of September 1961.,

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. THE PROCESS OF PRODUCING A PARTICULATE DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A NUCLEUS OF INORGANIC MATERIAL AND COATING OF A RELATIVELY NEUTRAL, REACTION-SET SALT OF A SYNTHETIC ORGANIC, ACIDIC WETTING AGENT, WHICH COMPRISES: SPRAYING SOLID PARTICULATE INORGANIC ALKALINE MATERIAL WHICH SERVES AS A DETERGENT BUILDER WITH ABOUT 0.5-50% BY WEIGHT, BASED ON THE WEIGHT OF THE REACTION MIXTURE, OF A SUBSTANTIALLY ANHYDROUS NORMALLY SLOW-REACTING MEMBER OF THE CLASS CONSISTING OF HIGHER ALKYL ARYL SULFONIC ACIDS, HIGHER ALKYL SULFONIC ACIDS, HIGHER ALKYL SULFURIC ACID ESTERS, THE ALKYL GROUPS IN SAID SULFONIC ACIDS AND SAID SULFURIC ACID ESTERS CONTAINING ABOUT 12-18 CARBON ATOMS AND ADMIXTURES THEREOF IN THE PRESENCE OF AT LEAST ABOUT 20% BY WEIGHT, BASED ON THE WEIGHT OF SAID REACTING MEMBERS, OF A SUBSTANTIALLY ANHYDROUS REACTION PROMOTING LIQUID CONSISTING ESSENTIALLY OF A MEMBER OF THE GROUP CONSISTING OF LOWER ALKYLENE GLYCOLS HAVING ABOUT 2-4 CARBON ATOMS, LOWER ALKYL ALCOHOLS HAVING ABOUT 1-4 CARBON ATOMS, CONCENTRATED SULFURIC ACID, AND ADMIXTURES THEREOF, WHEREBY SAID MEMBER IS COMPLETELY REACTED WITH SAID ALKALINE MATERIAL DURING A PERIOD OF UP TO ABOUT 5 MINUTES AND A DRY, SOLID, COATED, FINELY DIVIDED DETERGENT COMPOSITION IS PRODUCED AT ONCE DURING THE NEUTRALIZATION REACTION. 